WO2022054772A1 - Procédé de fabrication de composition de formation de motif d'impression, procédé de fabrication de produit durci, procédé de fabrication de motif d'impression, et procédé de fabrication de dispositif - Google Patents

Procédé de fabrication de composition de formation de motif d'impression, procédé de fabrication de produit durci, procédé de fabrication de motif d'impression, et procédé de fabrication de dispositif Download PDF

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Publication number
WO2022054772A1
WO2022054772A1 PCT/JP2021/032748 JP2021032748W WO2022054772A1 WO 2022054772 A1 WO2022054772 A1 WO 2022054772A1 JP 2021032748 W JP2021032748 W JP 2021032748W WO 2022054772 A1 WO2022054772 A1 WO 2022054772A1
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Prior art keywords
group
imprint pattern
composition
preferable
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PCT/JP2021/032748
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English (en)
Japanese (ja)
Inventor
旺弘 袴田
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2022547593A priority Critical patent/JP7470806B2/ja
Publication of WO2022054772A1 publication Critical patent/WO2022054772A1/fr
Priority to US18/179,820 priority patent/US20230219280A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/005—Surface shaping of articles, e.g. embossing; Apparatus therefor characterised by the choice of material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/002—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to a method for producing an imprint pattern forming composition, a method for producing a cured product, a method for producing an imprint pattern, and a method for producing a device.
  • the imprint method is a technique for transferring a fine pattern to a material by pressing a mold (generally also referred to as a mold or a stamper) on which a pattern is formed. Since it is possible to easily produce precise fine patterns by using the imprint method, it is expected to be applied in various fields in recent years, such as the field of precision processing for semiconductor integrated circuits. In particular, nanoimprint technology for forming nano-order-level fine patterns is drawing attention.
  • Patent Document 1 describes a liquid material for nanoimprint, characterized in that the number concentration of particles having a particle size of 0.07 ⁇ m or more is less than 310 particles / mL.
  • the imprint method As the imprint method, a method called a thermal imprint method or a curable imprint method has been proposed from the transfer method.
  • a thermal imprint method for example, a mold is pressed against a thermoplastic resin heated to a temperature higher than the glass transition temperature (hereinafter, may be referred to as “Tg”), and the mold is released after cooling to form a fine pattern.
  • Tg glass transition temperature
  • various materials can be selected in this method, there are problems that it is difficult to form a fine pattern because high pressure is required at the time of pressing and dimensional accuracy is lowered due to heat shrinkage or the like.
  • the imprint pattern forming composition is cured by light or heat in a state where the mold is pressed against the imprint pattern forming composition, and then the mold is released. Since it is imprinted on an uncured material, it is possible to omit part or all of high-pressure application and high-temperature heating, and it is possible to easily produce a fine pattern. In addition, since the dimensional fluctuation is small before and after curing, there is an advantage that a fine pattern can be formed with high accuracy.
  • a curable imprint method for example, after applying a composition for forming an imprint pattern on a support (which performs adhesion treatment such as formation of an adhesion layer if necessary), it is produced with a light-transmitting material such as quartz. There is a method of pressing the molded mold. The composition for forming an imprint pattern is cured by light irradiation with the mold pressed against it, and then the mold is released to produce a cured product to which the desired pattern is transferred.
  • an imprint pattern forming composition it is desired to reduce the number of foreign substances in the composition, for example, for the purpose of improving the inkjet ejection property at the time of application, improving the coating surface shape, and the like.
  • the present invention relates to a method for producing an imprint pattern forming composition in which the number of foreign substances contained in the obtained imprint pattern forming composition is reduced, a method for producing a cured product composed of the above imprint pattern forming composition, and the above. It is an object of the present invention to provide a method for producing an imprint pattern using an imprint pattern forming composition, and a method for producing a device including the above method for producing an imprint pattern.
  • ⁇ 1> Including a filtration step of filtering the precursor composition to obtain a composition for forming an imprint pattern.
  • the speed at which the precursor composition passes through the filter does not continuously exceed 0.9 cm / h for 10 seconds or more.
  • a method for producing a composition for forming an imprint pattern ⁇ 2> The method for producing an imprint pattern forming composition according to ⁇ 1>, wherein the filtration pressure in the filtration step is 0.20 MPa or less.
  • ⁇ 3> The method for producing an imprint pattern forming composition according to ⁇ 1> or ⁇ 2>, wherein the pore diameter of the filter used in the filtration step is 50 nm or less.
  • ⁇ 4> The method for producing an imprint pattern forming composition according to any one of ⁇ 1> to ⁇ 3>, wherein the filter contains a polyethylene-based resin, a nylon-based resin, or a fluorine-based resin.
  • the composition for forming an imprint pattern does not contain a solvent, or contains a solvent, and the content of the solvent exceeds 0% by mass with respect to the total mass of the composition for forming an imprint pattern.
  • the method for producing an imprint pattern forming composition according to any one of ⁇ 1> to ⁇ 4> which is less than 5% by mass.
  • the composition for forming an imprint pattern contains a solvent, and the content of the solvent is 90 to 99.5% by mass with respect to the total mass of the composition for forming an imprint pattern, ⁇ 1> to ⁇ . 4> The method for producing an imprint pattern forming composition according to any one of. ⁇ 7> The method for producing an imprint pattern forming composition according to any one of ⁇ 1> to ⁇ 6>, wherein the imprint pattern forming composition contains a polymerizable compound. ⁇ 8> In the method for producing an imprint pattern forming composition, the maximum speed at which the precursor composition before filtration or the composition for forming an imprint pattern after filtration is provided is 0.2 cm / h or more, ⁇ 1.
  • a curing step using the above-mentioned composition for forming an imprint pattern as a cured product and A method for manufacturing an imprint pattern, which comprises a peeling step of peeling the mold and the cured product.
  • a method for producing an imprint pattern forming composition in which the number of foreign substances contained in the obtained imprint pattern forming composition is reduced, and a method for producing a cured product comprising the above-mentioned imprint pattern forming composition are provided.
  • the numerical range represented by the symbol "-” means a range including the numerical values before and after "-” as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended action of the process can be achieved.
  • the notation that does not describe a substituted or unsubstituted group with respect to a group (atomic group) means that a group having a substituent (atomic group) is included as well as a group having no substituent (atomic group). be.
  • alkyl group when simply described as “alkyl group”, this includes both an alkyl group having no substituent (unsubstituted alkyl group) and an alkyl group having a substituent (substituted alkyl group). It means.
  • exposure means not only drawing using light but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified.
  • energy rays used for drawing include emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, active rays such as extreme ultraviolet rays (EUV light) and X rays, and particle beams such as electron beams and ion beams. Be done.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacrylic", or.
  • Any, and “(meth) acryloyl” means both “acryloyl” and “methacrylic", or either.
  • the solid content in the composition means other components other than the solvent, and the content (concentration) of the solid content in the composition is, unless otherwise specified, based on the total mass of the composition. It is expressed by the mass percentage of other components excluding the solvent.
  • the temperature is 23 ° C.
  • the atmospheric pressure is 101325 Pa (1 atmospheric pressure)
  • the relative humidity is 50% RH.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are shown as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • Mw and Mn for example, HLC-8220 (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, and TSKgel are used as columns. It can be obtained by using Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • each layer constituting the laminated body is described as "upper” or “lower”, the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
  • imprint preferably refers to a pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to a pattern transfer having a size of approximately 10 nm to 100 ⁇ m (nanoimprint).
  • the method for producing an imprint pattern forming composition of the present invention includes a filtration step of filtering a precursor composition to obtain an imprint pattern forming composition, and the rate at which the precursor composition passes through a filter in the above filtration step is high. Do not exceed 0.9 cm / h continuously for 10 seconds or more.
  • an imprint pattern forming composition containing a small number of foreign substances can be obtained.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • a precursor composition in which the components contained in the imprint pattern forming composition are mixed is prepared, and then a filter treatment is performed for the purpose of removing foreign substances.
  • the present inventors have stated that when the passing speed of the composition in the filter is high, foreign matter (for example, foreign matter easily deformed by pressure such as gel-like foreign matter) may pass through the filter. discovered.
  • the present inventors adopt a condition in which filtration is performed at a low speed such that the speed at which the precursor composition of the composition for forming an imprint pattern passes through the filter does not continuously exceed 0.9 cm / h for 10 seconds or more in the filtration step.
  • an imprint pattern forming composition having a small amount of foreign matter can be obtained. It is considered to be excellent in shape (condition of the surface of the coating film). Further, according to the method for producing an imprint pattern forming composition of the present invention, an imprint pattern forming composition having a small amount of foreign matter can be obtained. Therefore, when the imprint pattern forming composition is stored, for example, it is minute.
  • Patent Document 1 does not describe or suggest that an imprint pattern forming composition having a small amount of foreign matter can be obtained by performing such a filtration step.
  • details of each step in the method for producing the composition for forming an imprint pattern of the present invention will be described.
  • the method for producing an imprint pattern forming composition of the present invention includes a filtration step of filtering a precursor composition to obtain an imprint pattern forming composition, and the rate at which the precursor composition passes through a filter in the above filtration step is high. Do not exceed 0.9 cm / h continuously for 10 seconds or more.
  • the precursor composition refers to a composition containing a plurality of types among the components contained in the composition for forming an imprint pattern, and may be a composition containing all the components contained in the composition for forming an imprint pattern. preferable.
  • the precursor composition is prepared, for example, by the precursor composition preparation step described later.
  • each filter may be the same, or the material, the surface area to be filtered, the thickness, the pore size, and the like may be different. Foreign matter can be efficiently removed by passing it through the filter more than once.
  • the speed when passing through the filter at least once should not exceed 0.9 cm / h continuously for 10 seconds or more, but the speed when passing through all the filters is the speed per hour. It is preferable that 0.9 cm is not continuously exceeded for 10 seconds or more.
  • the speed may be 0.9 cm or less per hour, but is preferably 0.7 cm or less per hour, and more preferably 0.6 cm or less.
  • the lower limit of the speed is not particularly limited, but may be, for example, 0.1 cm / h.
  • the means for passing the precursor composition through the filter twice or more is not particularly limited, but preferred examples include a method of circulating the composition in an apparatus including a filter, and passing a plurality of filters connected in series one or more times each. Examples thereof include a method of filtering with a certain filter and then re-filtering with the same or different filters, and a method of combining them.
  • the effective filtration area of the filter is preferably 300 cm 2 or more, more preferably 500 cm 2 or more, and even more preferably 1,000 cm 2 or more.
  • the upper limit is not particularly limited, but may be, for example, 50,000 cm 2 or less.
  • the filter passed through later has a smaller pore size. With such a configuration, foreign matter tends to be removed more effectively.
  • the filtration pressure (applied pressure) in the filtration step may vary depending on the material of the filter and the filtration device, the chemical structure of the components contained in the precursor composition, etc., but is preferably 0.5 MPa or less, preferably 0.3 MPa or less. It is more preferably 0.2 MPa or less, further preferably 0.1 MPa or less, and particularly preferably 0.1 MPa or less. By setting such a range, it is possible to more effectively prevent impurities particles from passing through the filter due to impurities.
  • the lower limit of the filtration pressure is not particularly limited, but is preferably 0.05 MPa or more.
  • the average flow rate of the precursor composition is preferably 20 cm 3 or more per minute, and more preferably 100 cm 3 to 250 cm 3 per minute.
  • the pore diameter of at least one type is preferably 100 nm or less, and the pore diameter of any of the filters is more preferably 100 nm or less.
  • the pore diameter is more preferably 50 nm or less, and further preferably 1 nm to 50 nm.
  • the material of the filter used in the present invention is not particularly specified, but at least one type, such as polypropylene-based resin, fluorine-based resin, polyethylene-based resin, and nylon-based resin, can be preferably used.
  • at least one type is preferably a filter containing a fluororesin or a filter containing a polyethylene resin from the viewpoint of foreign matter removal and the stability of the filter over time.
  • the filter preferably contains a polyethylene-based resin, a nylon-based resin, or a fluororesin.
  • the polyethylene-based resin include high-density polyethylene and ultra-high molecular weight polyethylene.
  • the nylon-based resin include known nylons such as nylon-6 and nylon-6,6.
  • the fluororesin include polytetrafluoroethylene and the like.
  • the filter examples include a membrane filter and a depth filter, and a known filter can be used without particular limitation, but a membrane filter is preferable.
  • a membrane filter By using the membrane filter, it is possible to prevent gel-like impurities and the like from passing through the filter while being deformed in the filter.
  • at least one type of filter used in the present invention is a filter cartridge obtained by processing a membrane filter into a pleated shape.
  • the pleated filter cartridge has an advantage in that it can manufacture a large effective filtration area.
  • the temperature of the precursor composition in the filtration step may or may not be adjusted.
  • filtration may be performed with the temperature of the precursor composition in the range of 10 ° C to 40 ° C, and it is also preferable to set the temperature to 15 ° C to 30 ° C.
  • the method for producing an imprint pattern forming composition of the present invention is realized by a known production apparatus.
  • the manufacturing apparatus used in the method for manufacturing the composition for forming an imprint pattern of the present invention is not particularly specified as long as the above filter is included, and known techniques can be adopted for other components. Specifically, for example, the technique described in Japanese Patent No. 4323074 can be referred to.
  • the maximum speed at which the precursor composition before filtration or the composition for forming an imprint pattern after filtration is provided is preferably 0.2 cm / h or more, and is 0. It is more preferably .4 cm / h or more, and further preferably 0.6 cm / h or more.
  • Examples of the maximum speed include the maximum speed in the line in the above-mentioned manufacturing apparatus.
  • the method for producing an imprint pattern forming composition of the present invention may include a step of preparing a precursor composition (also referred to as a "precursor composition preparation step").
  • the step of preparing the precursor composition is preferably a step of mixing each component contained in the composition for forming an imprint pattern.
  • the mixing method is not particularly limited, and a known method may be used. The mixing is carried out, for example, in the range of 0 ° C to 100 ° C, preferably in the range of 10 ° C to 40 ° C.
  • the method for producing an imprint pattern forming composition of the present invention may further include other steps other than the filtration step and the precursor composition preparation step. Examples of other steps include a step of removing a salt component or the like from the precursor composition using an ion exchange resin.
  • each component contained in the composition for forming an imprint pattern will be described.
  • the details of each component contained in the composition for forming an imprint pattern and the details of each component contained in the precursor composition are the same. That is, the component preferably contained in the imprint pattern forming composition is preferably also contained in the precursor composition, and the content thereof is the same in the imprint pattern forming composition and the precursor composition.
  • the composition for forming an imprint pattern preferably contains a polymerizable compound.
  • the polymerizable compound is preferably a radically polymerizable compound.
  • the type of the polymerizable group possessed by the polymerizable compound is not particularly specified, but a group having an ethylenically unsaturated group, a cyclic ether group (epoxide group, glycidyl group, oxetanyl group) and the like are exemplified, and an ethylenically unsaturated group is exemplified. Groups having are preferred.
  • Examples of the group having an ethylenically unsaturated group include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group, allyl group, vinylphenyl group and the like, and (meth). ) Acryloyl group or (meth) acryloyloxy group is more preferable, and acryloyl group or acryloyloxy group is further preferable.
  • the polymerizable group defined here is referred to as Qp.
  • the polymerizable compound is not particularly limited, but a compound having an extinction coefficient A of 1.8 L / (g ⁇ cm) or less and a weight average molecular weight of 800 or more, which will be described later, is preferable.
  • a polymerizable compound having an extinction coefficient A of 1.8 L / (g ⁇ cm) or less and a weight average molecular weight of 800 or more is also referred to as a “specific polymerizable compound”.
  • the specific polymerizable compound examples include a compound containing a silicon atom (Si) (silicon-containing compound), a compound containing a cyclic structure (ring-containing compound), and a dendrimer-type compound, and a silicon-containing compound or a ring-containing compound is preferable.
  • the contained compound is more preferable.
  • the composition for forming an imprint pattern may contain only the other polymerizable compounds described below without containing the specific polymerizable compound, or may contain other polymerizable compounds described below in addition to the specific polymerizable compounds. It may be contained.
  • absorption coefficient A the maximum value of the absorbance per unit mass in the wavelength region of 250 to 400 nm in an acetonitrile solution of a specific polymerizable compound.
  • the maximum value of the absorption coefficient A of the specific polymerizable compound is 1.8 L / (g ⁇ cm) or less, preferably 1.5 L / (g ⁇ cm) or less, and 1.2 L / (g ⁇ cm) or less. ) Or less, more preferably 1.0 L / (g ⁇ cm) or less.
  • the extinction coefficient A is preferably 0.8 L / (g ⁇ cm) or less, and more preferably 0.5 L / (g ⁇ cm) or less. , 0.2 L / (g ⁇ cm) or less, more preferably less than 0.01 L / (g ⁇ cm).
  • the lower limit is not particularly limited, but is preferably 0.0001 L / (g ⁇ cm) or more. In the composition of the present invention, it is considered that by setting the absorption coefficient A to the above upper limit value or less, the curability of the deep part of the pattern is improved and the resolution of the pattern is excellent.
  • the weight average molecular weight of the specific polymerizable compound is 800 or more, preferably 1,000 or more, more preferably 1,500 or more, and further preferably more than 2,000.
  • the upper limit of the weight average molecular weight is not particularly specified, but for example, 100,000 or less is preferable, 50,000 or less is more preferable, 10,000 or less is further preferable, 8,000 or less is further preferable, and 5,000 or less. Is even more preferable, 3,500 or less is even more preferable, and 3,000 or less is particularly preferable.
  • the silicon-containing compound examples include compounds having a silicone skeleton. Specific examples thereof include a compound having at least one of a D-unit siloxane structure represented by the following formula (S1) and a T-unit siloxane structure represented by the formula (S2).
  • S1 to RS3 independently represent a hydrogen atom or a monovalent substituent, and * independently represent a binding site with another structure. It is preferable that RS1 to RS3 are independently and monovalent substituents.
  • an aromatic hydrocarbon group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms
  • an aliphatic hydrocarbon group (1 to 24 carbon atoms
  • 1 to 12 is more preferable, 1 to 6 is more preferable)
  • a cyclic or chain (straight or branched) alkyl group (1 to 12 carbon atoms is preferable, 1 to 6 is more preferable).
  • 1 to 3 is more preferable) or a group containing a polymerizable group is preferable.
  • the structure of the silicon-containing compound include the following formulas (s-1) to (s-9) in terms of partial structure.
  • Q in the formula is a group containing the above-mentioned polymerizable group Qp.
  • a plurality of these structures may be present in the compound, or they may be present in combination.
  • the silicon-containing compound is preferably a reaction product of a silicone resin and a compound having a polymerizable group.
  • a reactive silicone resin is preferable.
  • the reactive silicone resin include the above-mentioned modified silicone resin having a silicone skeleton, for example, a monoamine-modified silicone resin, a diamine-modified silicone resin, a special amino-modified silicone resin, an epoxy-modified silicone resin, and an alicyclic epoxy-modified silicone resin.
  • the compound having a polymerizable group a compound having a polymerizable group and a group capable of reacting with an alkoxysilyl group or a silanol group is preferable, and a compound having a polymerizable group and a hydroxy group is more preferable.
  • the compound having the above-mentioned polymerizable group includes a polymerizable group and a group that reacts with an amino group, an epoxy group, a mercapto group, a carboxy group and the like contained in the above-mentioned modified silicone resin.
  • a compound having the above may be used.
  • the preferred embodiment of the polymerizable group in the compound having a polymerizable group is the same as the preferred embodiment of the polymerizable group in the above-mentioned polymerizable compound.
  • the compound having a polymerizable group hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. More specifically, it may be a reaction product of a compound having a polymerizable group and a group capable of reacting with an alkoxysilyl group or a silanol group (for example, a hydroxy group) and a silicone resin having an alkoxysilyl group or a silanol group. preferable.
  • ring-containing compound examples include an aromatic ring and an alicyclic.
  • aromatic ring examples include an aromatic hydrocarbon ring and an aromatic heterocycle.
  • the aromatic hydrocarbon ring preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenalene ring, a fluorene ring, a benzocyclooctene ring, an acenaphthylene ring, a biphenylene ring, an indene ring, an indane ring, a triphenylene ring, and a pyrene. Examples thereof include a ring, a chrysene ring, a perylene ring, and a tetrahydronaphthalene ring.
  • the aromatic ring may have a structure in which a plurality of the aromatic rings are linked, and examples thereof include a biphenyl structure and a diphenylalkane structure (for example, 2,2-diphenylpropane).
  • the aromatic hydrocarbon ring specified here is referred to as aCy).
  • the aromatic heterocycle preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 5 carbon atoms.
  • thiophene ring examples include a thiophene ring, a furan ring, a dibenzofuran ring, a pyrrole ring, an imidazole ring, a benzimidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a thiaziazole ring, an oxadiazole ring, an oxazole ring, and a pyridine ring.
  • the aromatic heterocycle specified here is called hCy
  • the alicyclic has preferably 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • examples of the aliphatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cyclooctane ring, a dicyclopentadiene ring, and a spirodecane ring.
  • Examples of the aliphatic heterocycle include a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, an oxylan ring, an oxetane ring, an oxoran ring, an oxane ring, and a dioxane ring.
  • the alicyclic specified here is called fCy
  • the specific polymerizable compound when it is a ring-containing compound, it is preferably a compound containing an aromatic hydrocarbon ring, and more preferably a compound having a benzene ring.
  • a compound having a structure represented by the following formula (C-1) can be mentioned.
  • Ar represents the above aromatic hydrocarbon ring or aromatic heterocycle.
  • L 1 and L 2 are independently single bonds or linking groups, respectively.
  • the linking group an oxygen atom (oxy group), a carbonyl group, an amino group, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), or a group in which these are combined.
  • the (poly) alkyleneoxy group is preferable.
  • the (poly) alkyleneoxy group may be one having one alkyleneoxy group or one in which a plurality of alkyleneoxy groups are repeatedly linked. Further, the order of the alkylene group and the oxy group is not limited.
  • the number of repetitions of the alkyleneoxy group is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6.
  • R 3 is an arbitrary substituent, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). Is more preferable, 2 to 3 are more preferable), an aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), and an arylalkyl group (7 to 23 carbon atoms is preferable).
  • 7 to 19 is more preferable, 7 to 11 is more preferable), a hydroxy group, a carboxy group, an alkoxy group (preferably 1 to 24 carbon atoms, more preferably 1 to 12), and an acyl group (more preferably 1 to 6).
  • 2 to 12 carbon atoms are preferable, 2 to 6 are more preferable, 2 to 3 are more preferable, and an alkylcarbonyl group is preferable), an aryloyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable, and 7 is preferable.
  • ⁇ 11 is more preferable).
  • L 3 is a single bond or linking group. Examples of the linking group include the above L 1 and L 2 .
  • n3 is preferably 3 or less, more preferably 2 or less, further preferably 1 or less, and particularly preferably 0.
  • Q 1 and Q 2 are independently polymerizable groups, and the example of the above-mentioned polymerizable group Qp is preferable.
  • nq is preferably 2 or more.
  • the upper limit is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the substituents are arranged in series.
  • the specific polymerizable compound may be a dendrimer type compound.
  • Dendrimer means a dendritic polymer having a structure that branches regularly from the center.
  • a dendrimer is composed of a central molecule (stem) called a core and a side chain part (branch) called a dendron.
  • a fan-shaped compound is common, but it may be a dendrimer in which dendrons are spread in a semicircular or circular shape.
  • a group having a polymerizable group can be introduced into the dendron portion of the dendrimer (for example, the terminal portion away from the core) to obtain a polymerizable compound.
  • a dendrimer-type polyfunctional (meth) acrylate can be obtained.
  • the dendrimer type compound for example, the matters disclosed in Japanese Patent No. 5512970 can be referred to, and the description of the above-mentioned publication is incorporated in the present specification.
  • the specific polymerizable compound preferably has a polymerizable group equivalent of 130 or more, more preferably 150 or more, further preferably 160 or more, further preferably 190 or more, and 240 or more. It is even more preferable to have.
  • the upper limit of the polymerizable group equivalent is preferably 2,500 or less, more preferably 1,800 or less, further preferably 1,000 or less, and even more preferably 500 or less. , 350 or less, more preferably 300 or less.
  • the polymerizable group equivalent of the specific polymerizable compound is at least the above lower limit, the elastic modulus at the time of curing is in an appropriate range, and it is considered that the releasability is excellent.
  • the polymerizable group equivalent is not more than the above upper limit value, the crosslink density of the cured product pattern is in an appropriate range, and it is considered that the resolution of the transfer pattern is excellent.
  • the number of polymerizable groups in the specific polymerizable compound is preferably 2 or more, more preferably 3 or more, and preferably 4 or more in one molecule. More preferred.
  • the upper limit is preferably 50 or less, more preferably 40 or less, further preferably 30 or less, and even more preferably 20 or less.
  • the number is two or more in one molecule.
  • the upper limit is preferably 4 or less, and more preferably 3 or less.
  • the number is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more in one molecule.
  • the upper limit is preferably 1000 or less, more preferably 500 or less, and even more preferably 200 or less.
  • the viscosity of the specific polymerizable compound at 23 ° C. is preferably 100 mPa ⁇ s or more, more preferably 120 mPa ⁇ s or more, and even more preferably 150 mPa ⁇ s or more.
  • the upper limit of the viscosity is preferably 2000 mPa ⁇ s or less, more preferably 1500 mPa ⁇ s or less, and further preferably 1200 mPa ⁇ s or less.
  • the viscosity in the present specification is adjusted to 23 ° C. using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34' ⁇ R24). And the value measured. Other details regarding the measurement are in accordance with JISZ8803: 2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.
  • the composition for forming an imprint pattern may contain a polymerizable compound other than the specific polymerizable compound as the polymerizable compound.
  • the other polymerizable compound may be a monofunctional polymerizable compound having one polymerizable group or a polyfunctional polymerizable compound having two or more polymerizable groups.
  • the composition for forming an imprint pattern preferably contains a polyfunctional polymerizable compound, and more preferably contains both a polyfunctional polymerizable compound and a monofunctional polymerizable compound.
  • the polyfunctional polymerizable compound preferably contains at least one of a bifunctional polymerizable compound and a trifunctional polymerizable compound, and more preferably contains at least one of the bifunctional polymerizable compounds.
  • the molecular weight of the other polymerizable compound is preferably less than 2,000, more preferably 1,500 or less, further preferably 1,000 or less, and may be 800 or less.
  • the lower limit is preferably 100 or more.
  • the number of polymerizable groups of the polyfunctional polymerizable compound, which is another polymerizable compound, is 2 or more, preferably 2 to 7, more preferably 2 to 4, further preferably 2 or 3, and even more preferably 2. ..
  • R 21 is a q-valent organic group
  • R 22 is a hydrogen atom or a methyl group
  • q is an integer of 2 or more.
  • q is preferably an integer of 2 or more and 7 or less, more preferably an integer of 2 or more and 4 or less, still more preferably 2 or 3, and even more preferably 2.
  • R 21 is preferably a divalent to 7-valent organic group, more preferably a divalent to tetravalent organic group, further preferably a divalent or trivalent organic group, and a divalent organic group. Is more preferable.
  • R 21 is preferably a hydrocarbon group having at least one linear, branched and cyclic structure.
  • the hydrocarbon group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
  • R 21 is a divalent organic group, it is preferably an organic group represented by the following formula (1-2).
  • Z 1 and Z 2 are preferably single bonds, —O—, —Alk—, or —Alk—O—, respectively.
  • Alk represents an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), and may have a substituent as long as the effects of the present invention can be obtained.
  • R 9 is preferably a single bond or a linking group selected from the following formulas (9-1) to (9-10) or a combination thereof. Above all, it is preferable that the linking group is selected from the formulas (9-1) to (9-3), (9-7), and (9-8).
  • R 101 to R 117 are arbitrary substituents. Among them, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) and an acryloyl group (preferably 7 to 21 carbon atoms, 7 to 15 carbon atoms, 7 to 11 carbon atoms are preferable). (More preferably), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), thienyl group, frill group, (meth) acryloyl group, (meth) acryloyloxy group, (more preferred).
  • Ar is an arylene group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), and specifically, a phenylene group, a naphthalene diyl group, an anthracene diyl group, a phenanthrene diyl group, and the like. Examples include the full orange yl group.
  • hCy 1 is a heterocyclic group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 2 to 5 carbon atoms), and a 5-membered ring or a 6-membered ring is more preferable.
  • heterocycle constituting hCy 1 include the above aromatic heterocycle hCy, pyrrolidone ring, tetrahydrofuran ring, tetrahydropyran ring, morpholine ring and the like, and among them, thiophene ring, furan ring and dibenzofuran ring.
  • n and m are natural numbers of 100 or less, preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
  • p is an integer of 0 or more and less than or equal to the maximum number that can be substituted for each ring. In each case, the upper limit value is preferably half or less of the maximum number of substitutables, more preferably 4 or less, and further preferably 2 or less.
  • the polyfunctional polymerizable compound is preferably represented by the following formula (2-1).
  • R 9 , Z 1 and Z 2 are synonymous with R 9 , Z 1 and Z 2 in the formula (1-2), respectively, and the preferable range is also the same.
  • These polyfunctional polymerizable compounds may contain only one kind or two or more kinds.
  • the type of atom constituting the polyfunctional polymerizable compound used in the present invention is not particularly specified, but it is preferably composed of only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom, and a carbon atom. It is more preferable that the atom is composed only of an atom selected from an oxygen atom and a hydrogen atom.
  • the polyfunctional polymerizable compound preferably has a polymerizable group equivalent of 150 or more, more preferably 160 or more, further preferably 190 or more, and 240 or more. It is more preferable to have.
  • the upper limit is preferably 2,500 or less, more preferably 1,800 or less, and even more preferably 1,000 or less.
  • the polyfunctional polymerizable compound preferably has a cyclic structure.
  • the cyclic structure include an aromatic hydrocarbon ring aCy, an aromatic heterocycle hCy, and an alicyclic fCy.
  • Examples of other polymerizable compounds include the compounds described in paragraphs 0017 to 0024 and Examples of JP-A-2014-090133, the compounds described in paragraphs 0024-0088 of JP-A-2015-009171, and JP-A-2015.
  • the compounds described in paragraphs 0023 to 0037 of the publication No. 070145 and the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016/152597 can be mentioned, and these are incorporated herein by reference.
  • the type of the monofunctional polymerizable compound used in the present invention is not particularly defined as long as it does not deviate from the gist of the present invention.
  • the monofunctional polymerizable compound used in the present invention preferably has a cyclic structure or has a linear or branched hydrocarbon chain having 4 or more carbon atoms. In the present invention, only one type of monofunctional polymerizable compound may be contained, or two or more types may be contained.
  • the monofunctional polymerizable compound used in the present invention is preferably liquid at 25 ° C.
  • the liquid at 25 ° C. means a compound having fluidity at 25 ° C., for example, a compound having a viscosity at 25 ° C. of 1 to 100,000 mPa ⁇ s.
  • the viscosity of the monofunctional polymerizable compound at 25 ° C. is, for example, more preferably 10 to 20,000 mPa ⁇ s, and even more preferably 100 to 15,000 mPa ⁇ s.
  • the term "substantially free of solvent” means, for example, that the content of the solvent in the composition for forming an imprint pattern is 5% by mass or less, and further means that it is 3% by mass or less. In particular, it means that it is 1% by mass or less.
  • the viscosity of the monofunctional polymerizable compound used in the present invention at 25 ° C. is preferably 100 mPa ⁇ s or less, more preferably 10 mPa ⁇ s or less, further preferably 8 mPa ⁇ s or less, still more preferably 6 mPa ⁇ s or less. By setting the viscosity of the monofunctional polymerizable compound at 25 ° C.
  • the lower limit is not particularly specified, but may be, for example, 1 mPa ⁇ s or more.
  • the monofunctional polymerizable compound used in the present invention is preferably a monofunctional (meth) acrylic monomer, and more preferably a monofunctional acrylate.
  • the type of atom constituting the monofunctional polymerizable compound used in the present invention is not particularly specified, but it is preferably composed of only an atom selected from a carbon atom, an oxygen atom, a hydrogen atom and a halogen atom, and a carbon atom. It is more preferable that the atom is composed only of an atom selected from an oxygen atom and a hydrogen atom.
  • the monofunctional polymerizable compound used in the present invention preferably has a plastic structure.
  • at least one of the monofunctional polymerizable compounds used in the present invention contains one group selected from the group consisting of the following (1) to (3).
  • (1) A group containing at least one of an alkyl chain and an alkenyl chain and at least one of an alicyclic structure and an aromatic ring structure and having a total carbon number of 7 or more (hereinafter referred to as "group of (1)").
  • group of (1) A group containing an alkyl chain having 4 or more carbon atoms
  • group of (2) A group containing an alkenyl chain having 4 or more carbon atoms
  • (3) a group containing an alkenyl chain having 4 or more carbon atoms
  • the alkyl chain and the alkenyl chain in the groups (1) to (3) may be linear, branched, or cyclic, and are preferably linear or branched independently.
  • the groups (1) to (3) have at least one of the above-mentioned alkyl chain and alkenyl chain at the end of the monofunctional polymerizable compound, that is, at least one of the alkyl group and the alkenyl group. ..
  • the alkyl chain and the alkenyl chain may independently contain an ether group (—O—) in the chain, but it is preferable that the alkyl chain and the alkenyl chain do not contain an ether group from the viewpoint of improving releasability.
  • the group of the above (1) preferably has a total carbon number of 35 or less, and more preferably 10 or less.
  • a monocyclic ring or a fused ring having 3 to 8 membered rings is preferable.
  • the number of rings constituting the fused ring is preferably two or three.
  • the annular structure is more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Also, a single ring is more preferable.
  • cyclic structure in the group (1) a cyclohexane ring, a benzene ring and a naphthalene ring are more preferable, and a benzene ring is particularly preferable.
  • the annular structure is preferably an aromatic ring structure.
  • the number of cyclic structures in the group (1) may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a fused ring, the fused ring is considered as one cyclic structure.
  • the group (2) is a group containing an alkyl chain having 4 or more carbon atoms, and is preferably a group consisting only of an alkyl chain having 4 or more carbon atoms (that is, an alkyl group).
  • the number of carbon atoms in the alkyl chain is preferably 7 or more, and more preferably 9 or more.
  • the upper limit of the number of carbon atoms in the alkyl chain is not particularly limited, but may be, for example, 25 or less.
  • a compound in which a part of the carbon atom of the alkyl chain is replaced with a silicon atom can also be exemplified as a monofunctional polymerizable compound.
  • the group (3) is a group containing an alkenyl chain having 4 or more carbon atoms, and is preferably a group consisting only of an alkenyl chain having 4 or more carbon atoms (that is, an alkylene group).
  • the alkenyl chain preferably has 7 or more carbon atoms, and more preferably 9 or more carbon atoms.
  • the upper limit of the number of carbon atoms in the alkenyl chain is not particularly limited, but may be, for example, 25 or less.
  • the monofunctional polymerizable compound used in the present invention is preferably a compound in which one or more of the groups (1) to (3) above and the polymerizable group are directly bonded or via a linking group.
  • a compound in which any one of the groups (1) to (3) and the polymerizable group are directly bonded is more preferable.
  • monofunctional polymerizable compound examples include, but are not limited to, the compounds described in paragraph 0013 of International Publication No. 2018/025739 and the like.
  • the lower limit of the content of the monofunctional polymerizable compound with respect to the mass of the total polymerizable compound contained in the composition for forming an imprint pattern is 1.
  • mass or more is preferable, 3% by mass or more is more preferable, 5% by mass or more is further preferable, and 7% by mass or more is further preferable.
  • the upper limit is more preferably 29% by mass or less, more preferably 27% by mass or less, particularly preferably 25% by mass or less, further preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the amount of the monofunctional polymerizable compound By setting the amount of the monofunctional polymerizable compound to the above lower limit value or more with respect to the fully polymerizable compound, the mold releasability can be improved, and defects and mold breakage can be suppressed at the time of mold release. Further, when the value is not more than the above upper limit, the Tg of the cured film of the imprint pattern forming composition can be increased, and the etching processing resistance, particularly the waviness of the pattern at the time of etching can be suppressed.
  • a monofunctional polymerizable compound other than the above monofunctional polymerizable compound may be used as long as the gist of the present invention is not deviated, and among the polymerizable compounds described in JP-A-2014-170949, monofunctional compounds are used. Polymerizable compounds are exemplified and these contents are included herein.
  • the content of the polymerizable compound in the composition for forming an imprint pattern is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass, based on the total solid content of the composition.
  • the above is more preferable, and 95% by mass or more is particularly preferable.
  • the upper limit is preferably 99.9% by mass or less.
  • One type of the polymerizable compound may be used alone, or a plurality of types may be used in combination. When a plurality of types are used in combination, the total amount is preferably within the above range.
  • the composition for forming an imprint pattern preferably contains a polymerization initiator.
  • the polymerization initiator may be either a photopolymerization initiator or a thermal polymerization initiator, but is preferably a photopolymerization initiator from the viewpoint of realizing curing of the pattern by exposure.
  • the polymerization initiator may be a radical polymerization initiator or a cationic polymerization initiator, and the type of the polymerization initiator may be appropriately selected according to the type of the polymerizable compound. , And more preferably a photoradical polymerization initiator.
  • the maximum value of the molar extinction coefficient in the wavelength region of 250 to 400 nm in the acetonitrile solution of the photopolymerization initiator is referred to as "absorption coefficient B".
  • the maximum value of the absorption coefficient B of the polymerization initiator B is preferably 5,000 L / (mol ⁇ cm) or more, more preferably 10,000 L / (mol ⁇ cm) or more, and 25,000 L / (. It is more preferably mol ⁇ cm) or more.
  • the upper limit of the maximum value of the absorption coefficient B can be, for example, 100,000 L / (mol ⁇ cm) or less, and further, 50,000 L / (mol ⁇ cm) or less.
  • the photopolymerization initiator examples include an oxime ester-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an allyloylphosphine oxide-based photopolymerization initiator, and an alkylphenone-based photopolymerization initiator.
  • an oxime ester-based photopolymerization initiator refers to a compound having a linked structure of the following formula (1) in the molecule, and preferably has a linked structure of the formula (2). * In the formula represents a bond that binds to an organic group.
  • the molecular weight of the photopolymerization initiator is not particularly limited, but is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more.
  • the upper limit is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less.
  • Specific examples of the photopolymerization initiator include IRGACURE819, OXE-01, OXE-02, OXE-04, Darocure1173, IrgureTPO manufactured by BASF, NCI-831 and NCI-831E manufactured by ADEKA.
  • the composition for forming an imprint pattern may contain a thermal polymerization initiator.
  • the thermal polymerization initiator may be selected depending on the type of the polymerizable compound, but a thermal radical polymerization initiator is preferable.
  • the imprint pattern forming composition contains a thermal polymerization initiator, for example, the imprint pattern forming composition is heated while being pressed between the mold and the support to obtain a patterned cured product.
  • the composition for forming an imprint pattern may contain a photopolymerization initiator and a thermal polymerization initiator. Specific examples of the thermal polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • the content of the polymerization initiator is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and more preferably 2.0, based on the total solid content of the composition for forming an imprint pattern. It is more preferably mass% or more.
  • the upper limit value is preferably 8.0% by mass or less, and more preferably 6.0% by mass or less. When the content of the polymerization initiator is at least the above lower limit value, sufficient curability can be ensured and good resolution can be exhibited. On the other hand, when the value is not more than the above upper limit, it is possible to prevent the initiator from precipitating and inducing coating defects during coating or refrigerated storage.
  • One kind or a plurality of polymerization initiators may be used. When using a plurality of items, the total amount is within the above range.
  • the composition for forming an imprint pattern preferably contains a mold release agent.
  • the content of the release agent is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and 0. 6% by mass or more is more preferable.
  • the upper limit is less than 1.0% by mass, preferably 0.9% by mass or less, and more preferably 0.85% by mass or less.
  • the value is not more than the above upper limit, the pattern strength at the time of curing is not excessively lowered due to the influence of the release agent, and the synergistic effect with the polymerizable compound and the polymerization initiator is exhibited, and the good resolution is obtained. Can be realized.
  • One type or a plurality of mold release agents may be used. When using a plurality of items, the total amount is within the above range.
  • the type of the mold release agent is not particularly limited, but it is preferable that it has a function of segregating at the interface with the mold and effectively promoting the mold release with the mold. In the present invention, it is preferable that the mold release agent is substantially free of fluorine atoms and silicon atoms.
  • the term "substantially free” means that the total amount of fluorine atoms and silicon atoms is 1% by mass or less of the mold release agent, preferably 0.5% by mass or less, more preferably 0.1% by mass or less. It is more preferably 0.01% by mass or less.
  • the release agent used in the present invention is preferably a surfactant.
  • the alkylene glycol is preferably an alcohol compound having at least one hydroxy group at the terminal, or a compound having a (poly) alkylene glycol structure in which the hydroxy group is etherified ((poly) alkylene glycol compound).
  • the surfactant and the (poly) alkylene glycol compound are preferably non-polymerizable compounds having no polymerizable group Qp.
  • the (poly) alkylene glycol means that the alkylene glycol structure may be one or a plurality of the alkylene glycol structures may be repeatedly linked.
  • a nonionic surfactant is a compound having at least one hydrophobic moiety and at least one nonionic hydrophilic moiety.
  • the hydrophobic part and the hydrophilic part may be at the end of the molecule or inside, respectively.
  • the hydrophobic portion is composed of, for example, a hydrocarbon group, and the number of carbon atoms in the hydrophobic portion is preferably 1 to 25, more preferably 2 to 15, further preferably 4 to 10, and even more preferably 5 to 8.
  • the nonionic hydrophilic part includes an alcoholic hydroxy group, a phenolic hydroxy group, an ether group (preferably (poly) alkyleneoxy group, a cyclic ether group), an amide group, an imide group, a ureido group, a urethane group, a cyano group, and a sulfonamide. It is preferable to have at least one group selected from the group consisting of a group, a lactone group, a lactam group and a cyclocarbonate group. Among them, a compound having an alcoholic hydroxy group and an ether group (preferably a (poly) alkyleneoxy group and a cyclic ether group) is more preferable.
  • Alcohol compound, (poly) alkylene glycol compound As a preferable mold release agent used in the composition for forming an imprint pattern, as described above, an alcohol compound having at least one hydroxy group at the terminal or a (poly) alkylene glycol compound having an etherified hydroxy group is used. Can be mentioned.
  • the (poly) alkylene glycol compound preferably has an alkyleneoxy group or a polyalkyleneoxy group, and more preferably has a (poly) alkyleneoxy group containing an alkylene group having 1 to 6 carbon atoms. Specifically, it preferably has a (poly) ethyleneoxy group, a (poly) propyleneoxy group, a (poly) butyleneoxy group, or a mixed structure thereof, and preferably has a (poly) ethyleneoxy group, a (poly) propyleneoxy group, Alternatively, it has a mixed structure thereof, more preferably, and further preferably having a (poly) propyleneoxy group.
  • the (poly) alkylene glycol compound may be composed of substantially only the (poly) alkyleneoxy group except for the substituent at the terminal.
  • substantially means that the components other than the (poly) alkyleneoxy group are 5% by mass or less, preferably 1% by mass or less.
  • the (poly) alkylene glycol compound contains a compound consisting substantially only of the (poly) propyleneoxy group.
  • the number of repetitions of the alkyleneoxy group in the (poly) alkylene glycol compound is preferably 3 to 100, more preferably 4 to 50, further preferably 5 to 30, and 6 to 20. Is even more preferable.
  • the (poly) alkylene glycol compound may have a hydroxy group at the remaining terminal as long as the hydroxy group at the terminal is etherified, or may have a hydrogen atom substituted at the terminal hydroxy group.
  • an alkyl group that is, (poly) alkylene glycol alkyl ether
  • an acyl group that is, (poly) alkylene glycol ester
  • Compounds having a plurality of (preferably two or three) (poly) alkylene glycol chains via a linking group can also be preferably used.
  • Preferred specific examples of the (poly) alkylene glycol compound are polyethylene glycol, polypropylene glycol (for example, manufactured by Wako Pure Chemical Industries, Ltd.), mono or dimethyl ether, mono or dibutyl ether, mono or dioctyl ether, mono or disetyl ether, mono.
  • Examples thereof include stearate ester, monooleic acid ester, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene lauryl ether, and trimethyl ethers thereof.
  • the (poly) alkylene glycol compound is preferably a compound represented by the following formula (P1) or (P2).
  • RP1 in the formula may be a chain or a cyclic group, and may be a linear group or a branched alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms).
  • RP2 and RP3 are hydrogen atoms or alkyl groups which may be chain or cyclic, linear or branched (preferably 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, still more preferably 3 to 12 carbon atoms).
  • p is preferably an integer of 1 to 24, more preferably an integer of 2 to 12.
  • R P4 is a q-valent linking group, preferably a linking group composed of an organic group, and preferably a linking group composed of a hydrocarbon.
  • a linking group having an alkane structure preferably 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, further preferably 2 to 6 carbon atoms
  • a linking group having an alkene structure (2 carbon atoms).
  • ⁇ 24 is preferable, 2 to 12 is more preferable, 2 to 6 is more preferable), and a linking group having an aryl structure (carbon number 6 to 22 is preferable, carbon number 6 to 18 is more preferable, and 6 to 10 is more preferable).
  • q is preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4.
  • the weight average molecular weight of the alcohol compound or (poly) alkylene glycol compound used as the release agent is preferably 150 to 6,000, more preferably 200 to 3,000, still more preferably 250 to 2,000, and 300 to 1 , 200 is more preferred.
  • Examples of commercially available (poly) alkylene glycol compounds that can be used in the present invention include Orfin E1010 (manufactured by Nisshin Chemical Industry Co., Ltd.) and Brij35 (manufactured by Kishida Chemical Co., Ltd.).
  • the composition for forming an imprint pattern preferably contains at least one of a polymerization inhibitor.
  • the polymerization inhibitor has a function of quenching (deactivating) reactive substances such as radicals generated from the photopolymerization initiator, and plays a role of suppressing the reaction of the composition for forming an imprint pattern at a low exposure amount. ..
  • the polymerization inhibitor can be sufficiently dissolved, and the above effects are likely to be exhibited.
  • polymerization inhibitor examples include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'.
  • -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-Phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-
  • polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.
  • Specific examples of commercially available polymerization inhibitors include Q-1300, Q-1301, TBHQ (manufactured by Wako Pure Chemical Industries, Ltd.), Kinopower Series (manufactured by Kawasaki Kasei Chemicals Co., Ltd.), and the like.
  • the following compounds can be used (Me is a methyl group).
  • the content of the polymerization inhibitor is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass.
  • this content is at least the above lower limit, the reactivity of the photopolymerization initiator can be effectively exhibited. Further, by setting the value to the upper limit or less, it is possible to prevent the transfer pattern from collapsing and to enable effective patterning.
  • One kind or a plurality of polymerization inhibitors may be used. When a plurality of items are used, it is preferable that the total amount is within the above range.
  • the composition for forming an imprint pattern may contain a solvent.
  • the solvent is a compound that is liquid at 23 ° C and has a boiling point of 250 ° C or lower.
  • the content thereof is, for example, preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more.
  • the content is, for example, preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less.
  • the first preferred embodiment of the composition for forming an imprint pattern contains a solvent, and the content of the solvent is 90.0 to 99.5 mass with respect to the total mass of the composition for forming an imprint pattern. %.
  • the content of the solvent is preferably 95.0% by mass or more, more preferably 97.0% by mass or more.
  • the imprint pattern forming composition preferably contains the above-mentioned specific polymerizable compound as the polymerizable compound.
  • the second preferred embodiment of the composition for forming an imprint pattern is that it does not contain a solvent or contains a solvent, and the content of the solvent is 0 mass with respect to the total mass of the composition for forming an imprint pattern. % Is more than 5% by mass and less than 5% by mass.
  • the solvent is not contained or the content of the solvent is more than 0% by mass and less than 3% by mass, and the solvent is not contained or the content of the solvent is contained. Is more preferably more than 0% by mass and less than 1% by mass.
  • the imprint pattern forming composition preferably contains the above-mentioned other polymerizable compound as the polymerizable compound. In any of the above embodiments, only one type of solvent may be contained, or two or more types of solvent may be contained. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the boiling point of the component having the highest content of the solvent is preferably 200 ° C. or lower, more preferably 160 ° C. or lower.
  • the lower limit of the boiling point of the solvent is not particularly limited, but is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and even more preferably 100 ° C. or higher.
  • the solvent is preferably an organic solvent.
  • the solvent is preferably a solvent having any one or more of an ester group, a carbonyl group, an alkoxy group, a hydroxy group and an ether group.
  • alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate are selected.
  • Ru alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate are selected. Ru.
  • alkoxy alcohol examples include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), ethoxypropanol (for example, 1-ethoxy-2-propanol), and propoxypropanol (for example, 1-propanol-2- (Propanol), methoxybutanol (eg 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (For example, 4-methyl-2-pentanol) and the like.
  • methoxyethanol for example, 1-methoxy-2-propanol
  • ethoxypropanol for example, 1-ethoxy-2-propanol
  • propoxypropanol for example, 1-propanol-2- (Propanol)
  • methoxybutanol eg
  • propylene glycol monoalkyl ether carboxylate at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate is used. It is particularly preferable to have. Further, as the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable. As the lactic acid ester, ethyl lactate, butyl lactate, or propyl lactate is preferable.
  • acetic acid ester methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, or 3-methoxybutyl acetate are preferable.
  • alkoxypropionic acid ester methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
  • Chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetoneacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketones or methylamyl ketones are preferred.
  • As the cyclic ketone methylcyclohexanone, isophorone or cyclohexanone is preferable.
  • ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12 and even more preferably 7 to 10) and having a heteroatom number of 2 or less.
  • ester-based solvents having 7 or more carbon atoms and 2 or less heteroatomic atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate.
  • Examples thereof include isobutyl isobutyrate, heptyl propionate, butyl butanoate, and the like, and isoamyl acetate is particularly preferable. Further, it is also preferable to use one having a flash point (hereinafter, also referred to as fp) of 30 ° C. or higher.
  • fp flash point
  • Examples of such a component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), and methyl amyl ketone (fp: 42 ° C.).
  • propylene glycol monoethyl ether, ethyl lactate (EL), pentyl acetate or cyclohexanone are more preferable, and propylene glycol monoethyl ether or ethyl lactate is particularly preferable.
  • flash point means a value described in the reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co., Ltd. More preferred solvents include water, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, ⁇ -butyrolactone, butyl acetate, propylene glycol monomethyl ether (PGME), ethyl lactate and 4-methyl. At least one selected from the group consisting of -2-pentanol, more preferably at least one selected from the group consisting of PGMEA and PGME.
  • the composition for forming an imprint pattern may contain an ultraviolet absorber.
  • the ultraviolet absorber absorbs the leaked light (flare light) generated during exposure to suppress the reaction light from reaching the photopolymerization initiator, so that the reaction of the composition for forming an imprint pattern can be carried out at a low exposure amount. It plays a role of restraint.
  • Examples of the type of ultraviolet absorber include benzotriazole-based, triazine-based, cyanacrylate-based, benzophenone-based, and benzoate-based.
  • the content of the ultraviolet absorber is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass.
  • One kind or a plurality of ultraviolet absorbers may be used. When a plurality of items are used, it is preferable that the total amount is within the above range.
  • compositions for forming an imprint pattern may contain a sensitizer, an antioxidant, a colorant and the like.
  • the content is not particularly limited, but may be appropriately blended in an amount of about 0.01 to 20% by mass based on the total solid content of the composition.
  • the viscosity at 23 ° C. is preferably 20 mPa ⁇ s or less, more preferably 15 mPa ⁇ s or less, and 11 mPa ⁇ s or less. It is more preferably 9 mPa ⁇ s or less, and more preferably 9 mPa ⁇ s or less.
  • the lower limit of the viscosity is not particularly limited, but is preferably 5 mPa ⁇ s or more.
  • the viscosity (that is, the viscosity at the time of drying) when the solvent is removed from the composition for forming an imprint pattern is preferably 500 mPa ⁇ s or less, more preferably 400 mPa ⁇ s or less at 23 ° C.
  • Viscosity is measured, for example, according to the following method. The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34' ⁇ R24). The unit is mPa ⁇ s. Other details regarding the measurement are in accordance with JISZ8803: 2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.
  • the surface tension ( ⁇ Reist) of the imprint pattern forming composition at 23 ° C. is preferably 28 mN / m or more, more preferably 30 mN / m or more, and further preferably 32.0 mN / m or more. ..
  • the upper limit of the surface tension is not particularly limited, but is preferably 40 mN / m or less, more preferably 38 mN / m or less, and 36 mN / m from the viewpoint of imparting inkjet aptitude. It may be m or less.
  • the surface tension of the imprint pattern forming composition is measured according to the following method.
  • the surface tension was measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate.
  • the unit is expressed in mN / m. Two samples were prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.
  • the difference between the surface tension of the total solid content of the imprint pattern forming composition and the surface tension of the components of the imprint pattern forming composition excluding the mold release agent is 1.5 mN / m or less. It is preferably 1.0 mN / m or less, and even more preferably 0.8 mN / m or less.
  • the lower limit is preferably, for example, 0.01 mN / m or more, more preferably 0.1 mN / m or more. The smaller the difference, the better the compatibility of the release agent in the composition for forming an imprint pattern, and it becomes possible to form a homogeneous cured film.
  • the Onishi parameter of the composition for forming an imprint pattern is preferably 5 or less, more preferably 4 or less, and further preferably 3.7 or less.
  • the lower limit of the Onishi parameter of the composition for forming an imprint pattern is not particularly determined, but may be, for example, 1 or more, and further may be 2 or more.
  • the Onishi parameter can be obtained by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all the constituents into the following equations for the non-volatile components of the composition for forming an imprint pattern.
  • Onishi Parameter Sum of the number of carbon atoms, hydrogen atoms and oxygen atoms / (number of carbon atoms-number of oxygen atoms)
  • the composition for forming an imprint pattern preferably has a total amount of metal atoms and metal ions of 0.1% by mass or less with respect to the total solid content of the composition for forming an imprint pattern. , 0.01% by mass or less, more preferably 0.001% by mass or less.
  • the lower limit of the total amount is not particularly limited and may be 0% by mass.
  • the metal atoms and metal ions are contained in the composition for forming an imprint pattern as, for example, a metal complex, a metal salt compound, and other impurities derived from each component.
  • the metal is not particularly limited, but for example, iron, copper, titanium, lead, sodium, potassium, calcium, magnesium, manganese, aluminum, lithium, chromium, nickel, tin, zinc, arsenic, silver, gold, cadmium, etc.
  • Examples include cobalt, vanadium and tungsten.
  • the composition for forming an imprint pattern preferably has a total amount of inorganic compounds of 1% by mass or less, preferably 0.1% by mass, based on the total solid content of the composition for forming an imprint pattern. % Or less, more preferably 0.01% by mass or less.
  • the lower limit of the total amount is not particularly limited and may be 0% by mass.
  • the inorganic compound is not particularly limited, and examples thereof include an inorganic colorant such as an inorganic pigment, semi-metal particles such as silica particles, and metal particles such as titanium oxide particles.
  • the imprint pattern forming composition preferably has a total amount of salt compounds of 1% by mass or less, preferably 0.1% by mass, based on the total solid content of the imprint pattern forming composition. % Or less, more preferably 0.01% by mass or less.
  • the lower limit of the total amount is not particularly limited and may be 0% by mass.
  • the salt compound is not particularly limited, and examples thereof include compounds corresponding to colorants, acid generators, polymerization initiators, polymerizable compounds, resins, polymerization inhibitors, surfactants, and the like, and which include a salt structure. Be done.
  • the salt structure is not particularly limited, and examples thereof include a single salt structure, a double salt structure, and a complex salt structure.
  • a conventionally known storage container can be used as the storage container for the composition for forming an imprint pattern.
  • a storage container a multi-layer bottle composed of 6 types and 6 layers of resin and a 7-layer structure of 6 types of resin are used for the inner wall of the container for the purpose of suppressing impurities from being mixed into raw materials and compositions. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the method for producing an imprint pattern of the present invention comprises an application step of applying the composition for forming an imprint pattern of the present invention to an applied member selected from the group consisting of a support and a mold, the support and the mold.
  • the imprint pattern obtained by the method for producing an imprint pattern of the present invention is not particularly limited, but an imprint pattern including any of the shapes of lines, holes, and pillars is preferable. Above all, it is preferable that the obtained imprint pattern includes any shape of a line, a hole, or a pillar having a size of 100 nm or less.
  • the above size means the width of the line if it is a line, the minimum dimension of the hole portion if it is a hole, and the minimum dimension of the pillar if it is a pillar.
  • the method for producing an imprint pattern of the present invention includes an application step of applying the composition for forming an imprint pattern of the present invention to an applied member selected from the group consisting of a support and a mold.
  • an applied member selected from the group consisting of a support and a mold.
  • the imprint pattern forming composition of the present invention is applied onto the selected applied member.
  • the support and the mold one selected is the applied member and the other is the contact member. That is, in the application step, the composition for forming an imprint pattern of the present invention may be applied to the support and then brought into contact with the mold, or after being applied to the mold, the support (which has an adhesion layer or the like described later) may be provided. May be in contact with).
  • silicon substrate glass substrate, sapphire substrate, silicon carbide (silicon carbide) substrate, gallium nitride substrate, metal aluminum substrate, amorphous aluminum oxide substrate, polycrystalline aluminum oxide substrate, GaAsP, GaP, AlGaAs, InGaN, GaN. , AlGaN, ZnSe, AlGaInP, or ZnO.
  • the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass.
  • a silicon substrate is preferable as the substrate.
  • the support is preferably a member having an adhesion layer on the surface on the side to which the composition for forming an imprint pattern is applied.
  • the adhesion layer is preferably an adhesion layer formed by applying a composition for forming an adhesion layer, which will be described later, to a support.
  • the support may further be provided with a liquid film described later on the surface of the adhesion layer opposite to the side in contact with the support.
  • the liquid film is preferably a liquid film formed by applying a liquid film forming composition described later on the adhesion layer.
  • adhesion layer examples include those described in paragraphs 0017 to 0068 of JP2014-024322, paragraphs 0016 to 0044 of JP2013-093552A, and adhesion described in JP-A-2014-093385.
  • a layer, an adhesion layer described in JP-A-2013-202982, and the like can be used, and the contents thereof are incorporated in the present specification.
  • the mold is not particularly limited in the present invention.
  • the description in paragraphs 0105 to 0109 of JP2010-109092 (corresponding US application is the specification of US Patent Application Publication No. 2011/0199592) can be referred to, and these contents are incorporated in the present specification.
  • a quartz mold is preferable.
  • the mold pattern (line width) used in the present invention preferably has a size of 50 nm or less.
  • the mold pattern can be formed according to a desired processing accuracy by, for example, photolithography or an electron beam drawing method, but in the present invention, the mold pattern manufacturing method is not particularly limited.
  • a mold in which an imprint pattern including any of the shapes of lines, holes, and pillars is formed is preferable. Above all, a mold in which an imprint pattern including any shape of a line, a hole, or a pillar having a size of 100 nm or less is formed is preferable.
  • the method for applying the composition for forming an imprint pattern of the present invention to the applied member is not particularly specified, and a generally well-known application method can be adopted.
  • a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scan method, and an inkjet method are exemplified.
  • the inkjet method and the spin coating method are preferably mentioned.
  • the composition for forming an imprint pattern may be applied by multiple coating.
  • the volume of the droplets is preferably about 1 to 20 pL, and it is preferable to arrange the droplets on the surface of the support at intervals.
  • the droplet interval may be appropriately set according to the volume of the droplet, but an interval of 10 to 1000 ⁇ m is preferable.
  • the droplet spacing is the placement spacing of the inkjet nozzles.
  • the inkjet method has an advantage that the loss of the composition for forming an imprint pattern is small. Specific examples of the method for applying the composition for forming an imprint pattern by an inkjet method include the methods described in JP-A-2015-179807, International Publication No.
  • the spin coating method has the advantage that the coating process is highly stable and the choice of materials that can be used is expanded.
  • Specific examples of the method for applying the composition for forming an imprint pattern by the spin coating method include the methods described in JP2013-09583A, JP2015-071741 and the like, and the methods described in these documents. Can also be suitably used in the present invention.
  • the method for producing an imprint pattern of the present invention may further include a drying step of drying the composition for forming an imprint pattern of the present invention applied by the application step.
  • a drying step In the drying step, at least a part of the solvent contained in the applied composition for forming an imprint pattern of the present invention is removed.
  • the drying method is not particularly limited, and drying by heating, drying by blowing air, or the like can be used without particular limitation, but drying by heating is preferable.
  • the heating means is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used.
  • a layer formed from an imprint pattern forming composition after an application step and a drying step performed as necessary, and a layer before the contact step is also referred to as a "pattern forming layer".
  • a member not selected as an applied member from the group consisting of the support and the mold is used as a contact member in the imprint pattern forming composition (pattern forming layer). Includes a contact step to bring them into contact.
  • the support is selected as the applied member in the above application step
  • the contact step the surface to which the imprint pattern forming composition of the present invention of the present invention is applied (the surface on which the pattern forming layer is formed) is covered with the support.
  • the mold which is a contact member, is brought into contact with each other.
  • the contact step the contact member is applied to the surface of the mold to which the imprint pattern forming composition of the present invention is applied (the surface on which the pattern forming layer is formed).
  • the support that is is brought into contact. That is, by the contact step, the composition for forming an imprint pattern of the present invention is present between the applied member and the contact member. Details of the support and mold are as described above.
  • the pressing pressure is preferably 1 MPa or less.
  • the support and the mold are less likely to be deformed, and the pattern accuracy tends to be improved. It is also preferable because the pressing force is low and the device tends to be miniaturized.
  • the pattern forming layer and the contact member are brought into contact with each other in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.
  • the method for producing an imprint pattern of the present invention includes a curing step of using the above-mentioned composition for forming an imprint pattern as a cured product.
  • the curing step is performed after the contacting step and before the peeling step.
  • the method for producing a cured product of the present invention includes a step of curing the composition for forming an imprint pattern obtained by the method for producing a composition for forming an imprint pattern of the present invention.
  • the curing step can be performed by the same method as the curing step in the method for producing an imprint pattern of the present invention.
  • the cured product is preferably a cured product in which the mold has been peeled off by the peeling step described later.
  • the curing method examples include curing by heating, curing by exposure, and the like, which may be determined according to the type of polymerization initiator contained in the composition for forming an imprint pattern, but curing by exposure is preferable.
  • the polymerization initiator is a photopolymerization initiator
  • the composition for forming an imprint pattern can be cured by performing exposure in the curing step.
  • the exposure wavelength is not particularly limited and may be determined according to the polymerization initiator, but for example, ultraviolet light or the like can be used.
  • the exposure light source may be determined according to the exposure wavelength, but g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broadband light (three wavelengths of g, h, and i-line), and , Light containing light of at least two wavelengths selected from the group consisting of light having a wavelength shorter than i-line. For example, a high-pressure mercury lamp when an optical filter is not used, etc.), a semiconductor laser (wavelength).
  • the irradiation amount (exposure amount) at the time of exposure may be sufficiently larger than the minimum irradiation amount required for curing the composition for forming an imprint pattern.
  • the irradiation amount required for curing the imprint pattern forming composition can be appropriately determined by examining the consumption amount of unsaturated bonds of the imprint pattern forming composition and the like.
  • the exposure amount is preferably in the range of, for example, 5 to 1,000 mJ / cm 2 , and more preferably in the range of 10 to 500 mJ / cm 2 .
  • the exposure illuminance is not particularly limited and may be selected depending on the relationship with the light source, but is preferably in the range of 1 to 500 mW / cm 2 , and more preferably in the range of 10 to 400 mW / cm 2 .
  • the exposure time is not particularly limited and may be determined in consideration of the exposure illuminance according to the exposure amount, but is preferably 0.01 to 10 seconds, more preferably 0.5 to 1 second.
  • the temperature of the support during exposure is usually room temperature, but exposure may be performed while heating in order to enhance reactivity.
  • a vacuum state is used as a pre-exposure stage, it is effective in preventing air bubbles from being mixed in, suppressing a decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the composition for forming an imprint pattern. You may irradiate.
  • the preferred degree of vacuum during exposure is in the range of 10 -1 Pa to normal pressure.
  • the composition for forming an imprint pattern after the exposure may be heated, if necessary.
  • the heating temperature is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
  • the heating time is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
  • the composition for forming an imprint pattern can be cured by heating in the curing step.
  • the preferred embodiment of the heating temperature and the heating time is the same as the heating temperature and the heating time in the case of heating after the above exposure.
  • the heating means is not particularly limited, and examples thereof include heating means similar to the heating in the above-mentioned drying step.
  • the method for producing an imprint pattern of the present invention includes a peeling step of peeling the mold and the cured product.
  • the peeling step the cured product obtained by the curing step and the mold are peeled off, and a patterned cured product (also referred to as “cured product pattern”) to which the pattern of the mold is transferred is obtained.
  • the obtained cured product pattern can be used for various purposes as described later.
  • the present invention is particularly advantageous in that a nano-order fine cured product pattern can be formed, and further, a cured product pattern having a size of 50 nm or less, particularly 30 nm or less can be formed.
  • the lower limit of the size of the cured product pattern is not particularly specified, but it can be, for example, 1 nm or more.
  • the peeling method is not particularly limited, and for example, it can be performed by using a mechanical peeling device or the like known in the imprint pattern manufacturing method.
  • the method for manufacturing a device of the present invention includes a method for manufacturing an imprint pattern of the present invention.
  • the pattern (cured product pattern) formed by the method for manufacturing an imprint pattern of the present invention is used as a permanent film used for a liquid crystal display (LCD) or the like, or an etching resist (for lithography) for manufacturing a semiconductor element.
  • a method of manufacturing a device used as a mask) can be mentioned.
  • the present invention discloses a method for manufacturing a circuit board, which includes a step of obtaining a pattern (cured product pattern) by the method for manufacturing an imprint pattern of the present invention, and a method for manufacturing a device including the circuit board.
  • a step of etching or ion-implanting the substrate using the pattern (cured product pattern) obtained by the above pattern forming method as a mask and forming an electronic member are formed. It may have a step of performing.
  • the circuit board is preferably a semiconductor element. That is, the present invention discloses a method for manufacturing a semiconductor device including the method for manufacturing an imprint pattern of the present invention. Further, the present invention discloses a method for manufacturing a device having a step of obtaining a circuit board by the method of manufacturing the circuit board and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
  • a polarizing plate having a large screen size for example, 55 inches or more than 60 inches
  • the present invention discloses a method for manufacturing a polarizing plate including the method for manufacturing an imprint pattern of the present invention and a method for manufacturing a device including the above-mentioned polarizing plate.
  • the polarizing plate described in JP-A-2015-132825 and International Publication No. 2011/132649 can be manufactured.
  • 1 inch is 25.4 mm.
  • the pattern (cured product pattern) produced by the method for producing an imprint pattern of the present invention is also useful as an etching resist (mask for lithography). That is, the present invention discloses a method for manufacturing a device including the method for manufacturing an imprint pattern of the present invention and using the obtained cured product pattern as an etching resist.
  • a pattern (cured product pattern) is formed by applying the method for producing an imprint pattern of the present invention on a support, and the obtained cured product pattern is used.
  • An embodiment in which the support is etched by using it as an etching mask can be mentioned.
  • an etching gas such as hydrogen fluoride in the case of wet etching and CF 4 in the case of dry etching, a pattern along the shape of the desired cured product pattern is formed on the support. Can be done.
  • the pattern (cured product pattern) manufactured by the method for manufacturing an imprint pattern of the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state image pickup element, an LED (light emitting diode), and an organic EL (organic electro).
  • Luminescence and other light emitting elements, liquid crystal displays (LCD) and other optical devices, diffraction grids, relief holograms, optical waveguides, optical filters, microlens arrays and other optical components, thin films, organic transistors, color filters, antireflection films, etc.
  • polarizing plates polarizing elements
  • optical films flat panel display members
  • flat panel display members such as pillars, nanobiodevices, immunoanalytical chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and block copolymers.
  • DNA deoxyribonucleic acid
  • microreactors microreactors
  • photonic liquid crystals and block copolymers.
  • the present invention discloses a method for manufacturing these devices, including a method for manufacturing the imprint pattern of the present invention.
  • composition for forming an adhesive layer As described above, by providing the adhesion layer between the support and the imprint pattern forming composition, the effect of improving the adhesion between the support and the imprint pattern forming composition layer can be obtained.
  • the adhesion layer is obtained by applying the composition for forming an adhesion layer onto a support by the same method as the composition for forming an imprint pattern, and then curing the composition.
  • each component of the composition for forming an adhesive layer will be described.
  • the composition for forming an adhesive layer contains a curable component.
  • the curable component is a component constituting the adhesion layer, and may be either a high molecular weight component (for example, a molecular weight of more than 1000) or a low molecular weight component (for example, a molecular weight of less than 1000).
  • a resin, a cross-linking agent, and the like are exemplified. Each of these may be used alone or in combination of two or more.
  • the total content of the curable component in the composition for forming an adhesive layer is not particularly limited, but is preferably 50% by mass or more in the total solid content, and more preferably 70% by mass or more in the total solid content. It is more preferably 80% by mass or more in the total solid content.
  • the upper limit is not particularly limited, but is preferably 99.9% by mass or less.
  • the concentration of the curable component in the composition for forming an adhesive layer is not particularly limited, but is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. , 0.1% by mass or more is more preferable.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and further preferably less than 1% by mass.
  • the resin in the composition for forming the adhesion layer a known resin can be widely used.
  • the resin used in the present invention preferably has at least one of a radically polymerizable group and a polar group, and more preferably has both a radically polymerizable group and a polar group.
  • an adhesion layer having excellent strength can be obtained. Further, by having a polar group, the adhesion with the support is improved. Further, when a cross-linking agent is blended, the cross-linked structure formed after curing becomes stronger, and the strength of the obtained adhesion layer can be improved.
  • the radically polymerizable group preferably contains an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group include a (meth) acryloyl group (preferably a (meth) acryloyloxy group and a (meth) acryloylamino group), a vinyl group, a vinyloxy group, an allyl group, a methylallyl group and a propenyl group.
  • Butenyl group, vinylphenyl group, cyclohexenyl group, (meth) acryloyl group and vinyl group are preferable, (meth) acryloyl group is more preferable, and (meth) acryloyloxy group is further preferable.
  • the ethylenically unsaturated bond-containing group defined here is referred to as Et.
  • the polar group is at least an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, an acyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an alkoxycarbonylamino group, a sulfonamide group, a phosphoric acid group, a carboxy group and a hydroxy group. It is preferably one, more preferably at least one of an alcoholic hydroxy group, a phenolic hydroxy group and a carboxy group, and even more preferably an alcoholic hydroxy group or a carboxy group.
  • the polar group defined here is referred to as a polar group Po.
  • the polar group is preferably a nonionic group.
  • the resin in the composition for forming an adhesive layer may further contain a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group, and an epoxy group is preferable.
  • the cyclic ether group defined here is referred to as a cyclic ether group Cyt.
  • the resin examples include (meth) acrylic resin, vinyl resin, novolak resin, phenol resin, melamine resin, urea resin, epoxy resin, and polyimide resin, and at least one of (meth) acrylic resin, vinyl resin, and novolak resin. It is preferable to have.
  • the weight average molecular weight of the resin is preferably 4000 or more, more preferably 6000 or more, and further preferably 8000 or more.
  • the upper limit is preferably 1,000,000 or less, and may be 500,000 or less.
  • the resin preferably has at least one structural unit of the following formulas (1) to (3).
  • R 1 and R 2 are independently hydrogen atoms or methyl groups, respectively.
  • R 21 and R 3 are independent substituents.
  • L 1 , L 2 and L 3 are independently single bonds or linking groups, respectively.
  • n2 is an integer from 0 to 4.
  • n3 is an integer of 0 to 3.
  • Q 1 is an ethylenically unsaturated bond-containing group or a cyclic ether group.
  • Q 2 is an ethylenically unsaturated bond-containing group, a cyclic ether group or a polar group.
  • R 1 and R 2 are preferably methyl groups.
  • R 21 When there are a plurality of R 21 , they may be connected to each other to form an annular structure.
  • linkage means not only a mode of bonding and continuity, but also a mode of losing some atoms and condensing (condensing).
  • an oxygen atom, a sulfur atom, and a nitrogen atom (amino group) may be contained in the linked cyclic structure.
  • the cyclic structure formed includes an aliphatic hydrocarbon ring (the examples below are referred to as ring Cf) (for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl). Group, cyclohexenyl group, etc.), aromatic hydrocarbon ring (the one exemplified below is referred to as ring Cr) (benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.), nitrogen-containing heterocycle (exemplified below).
  • ring Cf aliphatic hydrocarbon ring
  • ring Cf for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopropenyl group, cyclobutenyl group, cyclopen
  • oxygen-containing hetero Rings examples below are referred to as ring Co
  • sulfur-containing heterocycle examples below are rings.
  • Cs) thiophene ring, thiirane ring, thietan ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, etc.
  • R3s When there are a plurality of R3s , they may be connected to each other to form an annular structure.
  • Examples of the cyclic structure formed include Cf, ring Cr, ring Cn, ring Co, and ring Cs.
  • L 1 , L 2 and L 3 are independently single-bonded or a linking group L described later.
  • a single bond, an alkylene group defined by the linking group L, or a (oligo) alkyleneoxy group is preferable, and an alkylene group is more preferable.
  • the linking group L preferably has a polar group Po as a substituent.
  • an embodiment in which the alkylene group has a hydroxy group as a substituent is also preferable.
  • the "(oligo) alkyleneoxy group” means a divalent linking group having one or more "alkyleneoxy" as a constituent unit.
  • the carbon number of the alkylene chain in the structural unit may be the same or different for each structural unit.
  • N2 is preferably 0 or 1, more preferably 0.
  • n3 is preferably 0 or 1, more preferably 0.
  • the ethylenically unsaturated bond-containing group Et is preferable.
  • a polar group is preferable, and an alkyl group having an alcoholic hydroxy group is preferable.
  • the above resin may further contain at least one of the following structural units (11), (21) and (31).
  • the constituent unit (11) is preferably combined with the constituent unit (1)
  • the constituent unit (21) is preferably combined with the constituent unit (2)
  • the constituent unit (31) is preferable.
  • R 11 and R 22 are independently hydrogen atoms or methyl groups, respectively.
  • R 17 is a substituent.
  • R 27 is a substituent.
  • n21 is an integer from 0 to 5.
  • R 31 is a substituent and n 31 is an integer of 0 to 3.
  • R 11 and R 22 are preferably methyl groups.
  • R 17 is preferably a group containing a polar group or a group containing a cyclic ether group.
  • R 17 is a group containing a polar group, it is preferably a group containing the above-mentioned polar group Po, and it is either the above-mentioned polar group Po or the above-mentioned substituent T substituted with the above-mentioned polar group Po. Is more preferable.
  • R 17 is a group containing a cyclic ether group, it is preferably a group containing the above-mentioned cyclic ether group Cyt, and more preferably a substituent T substituted with the above-mentioned cyclic ether group Cyt.
  • R 27 is preferably a substituent and at least one of R 27 is preferably a polar group.
  • the substituent T is preferably the substituent T.
  • n21 is preferably 0 or 1, more preferably 0. When there are a plurality of R 27s , they may be connected to each other to form an annular structure. Examples of the formed cyclic structure include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.
  • R 31 is preferably a substituent T.
  • n31 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. When there are a plurality of R 31 , they may be connected to each other to form an annular structure. Examples of the formed cyclic structure include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.
  • an alkylene group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms
  • an alkenylene group preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable.
  • (oligo) alkyleneoxy group the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 3; the number of repetitions is 1 to 50 is preferred, 1 to 40 is more preferred, 1 to 30 is even more preferred
  • an arylene group (6 to 22 carbon atoms is preferred, 6 to 18 is more preferred, 6 to 10 is even more preferred
  • an oxygen atom preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms
  • an alkenylene group preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable.
  • alkylene group, alkenylene group, and alkyleneoxy group may have the above-mentioned substituent T.
  • the alkylene group may have a hydroxy group.
  • the linking chain length of the linking group L is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6.
  • the alkylene group, alkenylene group, and (oligo) alkyleneoxy group defined by the linking group L may be chain-like or cyclic, and may be linear or branched.
  • the atom constituting the linking group L preferably contains a carbon atom, a hydrogen atom, and if necessary, a hetero atom (at least one selected from an oxygen atom, a nitrogen atom, and a sulfur atom).
  • the number of carbon atoms in the linking group is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6.
  • the hydrogen atom may be determined according to the number of carbon atoms and the like.
  • the number of heteroatoms is preferably 0 to 12, more preferably 0 to 6, and even more preferably 0 to 3, independently of the oxygen atom, nitrogen atom, and sulfur atom.
  • the above resin may be synthesized by a conventional method.
  • the resin having the structural unit of the formula (1) can be appropriately synthesized by a known method for addition polymerization of olefins.
  • the resin having the structural unit of the formula (2) can be appropriately synthesized by a known method for addition polymerization of styrene.
  • the resin having the structural unit of the formula (3) can be appropriately synthesized by a known method for synthesizing a phenol resin.
  • the above resin may be used alone or in combination of two or more.
  • the cross-linking agent in the composition for forming an adhesive layer is not particularly limited as long as it promotes curing by a cross-linking reaction.
  • the cross-linking agent preferably forms a cross-linked structure by reacting with the polar group of the resin. By using such a cross-linking agent, the resin is bonded more firmly and a stronger film can be obtained.
  • cross-linking agent examples include epoxy compounds (compounds having an epoxy group), oxetanyl compounds (compounds having an oxetanyl group), alkoxymethyl compounds (compounds having an alkoxymethyl group), methylol compounds (compounds having a methylol group), and blocks.
  • examples thereof include isocyanate compounds (compounds having a blocked isocyanate group), and alkoxymethyl compounds (compounds having an alkoxymethyl group) are preferable because they can form strong bonds at low temperatures.
  • composition for forming an adhesive layer may contain other components in addition to the above components.
  • the composition for forming an adhesive layer preferably contains a solvent (hereinafter, also referred to as “solvent for adhesive layer”).
  • the solvent is, for example, a compound that is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower.
  • the adhesive layer forming composition preferably contains 99.0% by mass or more of the adhesive layer solvent, more preferably 99.2% by mass or more, and may contain 99.4% by mass or more. That is, the composition for forming an adhesive layer preferably has a total solid content concentration of 1% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.6% by mass or less. ..
  • the lower limit is preferably more than 0% by mass, more preferably 0.001% by mass or more, further preferably 0.01% by mass or more, and 0.1% by mass or more. Is even more preferable.
  • the solvent may be contained in only one kind or two or more kinds in the composition for forming an adhesive layer. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
  • the boiling point of the adhesive layer solvent is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and 130 ° C. or lower. Is even more preferable.
  • the lower limit is preferably 23 ° C, more preferably 60 ° C or higher.
  • the solvent for the adhesive layer is preferably an organic solvent.
  • the solvent is preferably a solvent having at least one of an ester group, a carbonyl group, a hydroxy group and an ether group. Above all, it is preferable to use an aprotic polar solvent.
  • alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene Carbonates are mentioned, with propylene glycol monoalkyl ethers and lactones being particularly preferred.
  • thermoacid generator is a compound that generates an acid by heating and promotes cross-linking by the action of the acid. When used in combination with the above-mentioned cross-linking agent, a stronger adhesive layer can be obtained.
  • an organic onium salt compound in which a cation component and an anion component are paired is usually used. Examples of the cation component include organic sulfonium, organic oxonium, organic ammonium, organic phosphonium and organic iodinenium.
  • anion component examples include BF 4- , B (C 6 F 5 ) 4- , SbF 6- , AsF 6- , PF 6- , CF 3 SO 3- , C 4 F 9 SO 3- and (CF 3 SO 2 ) 3 C - can be mentioned.
  • thermoacid generator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the cross-linking agent. Only one kind of thermal acid generator may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the composition for forming a close contact layer may contain a polymerization initiator, and preferably contains at least one of a thermal polymerization initiator and a photopolymerization initiator. Further, the composition for forming a close contact layer does not have to contain a polymerization initiator. By including the polymerization initiator, the reaction of the polymerizable group contained in the composition for forming the adhesion layer is promoted, and the adhesion tends to be improved.
  • a photopolymerization initiator is preferable from the viewpoint of improving the cross-linking reactivity with the composition for forming an imprint pattern.
  • a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. Further, in the present invention, a plurality of types of photopolymerization initiators may be used in combination.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives and the like.
  • Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
  • the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification.
  • acylphosphine compound examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
  • the content of the photopolymerization initiator used in the adhesion layer forming composition is, for example, 0.0001 to 5% by mass, preferably 0.0005 to 3% by mass, based on the total solid content when blended. Yes, more preferably 0.01 to 1% by mass. When two or more kinds of photopolymerization initiators are used, the total amount thereof is within the above range.
  • a liquid film on the adhesion layer it is also preferable to form a liquid film on the adhesion layer by using a liquid film forming composition containing a radically polymerizable compound which is liquid at 23 ° C. and 1 atm.
  • the liquid film is obtained by applying the liquid film forming composition onto the support by the same method as the imprint pattern forming composition, and then drying the composition.
  • the adhesion between the support and the imprint pattern forming composition is further improved, and the wettability of the imprint pattern forming composition on the support is also improved.
  • the composition for forming a liquid film will be described.
  • the viscosity of the liquid film forming composition is preferably 1000 mPa ⁇ s or less, more preferably 800 mPa ⁇ s or less, further preferably 500 mPa ⁇ s or less, and more preferably 100 mPa ⁇ s or less. More preferred.
  • the lower limit of the viscosity is not particularly limited, but may be, for example, 1 mPa ⁇ s or more. Viscosity is measured according to the method below.
  • Viscosity is measured by adjusting the temperature of the sample cup to 23 ° C using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34'x R24). The unit is mPa ⁇ s. Other details regarding the measurement are in accordance with JISZ8803: 2011. Two samples are prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times is adopted as the evaluation value.
  • the liquid film forming composition contains a radically polymerizable compound (radical polymerizable compound A) that is liquid at 23 ° C. and 1 atm.
  • the viscosity of the radically polymerizable compound A at 23 ° C. is preferably 1 to 100,000 mPa ⁇ s.
  • the lower limit is preferably 5 mPa ⁇ s or more, and more preferably 11 mPa ⁇ s or more.
  • the upper limit is preferably 1000 mPa ⁇ s or less, and more preferably 600 mPa ⁇ s or less.
  • the radically polymerizable compound A may be a monofunctional radically polymerizable compound having only one radically polymerizable group in one molecule, or a polyfunctional radical having two or more radically polymerizable groups in one molecule. It may be a polymerizable compound. A monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound may be used in combination. Among them, the radically polymerizable compound A contained in the liquid film forming composition preferably contains a polyfunctional radically polymerizable compound for the reason of suppressing pattern collapse, and has 2 to 5 radically polymerizable groups in one molecule.
  • radical-polymerizable compound containing the radical-polymerizable compound it is more preferable to contain a radical-polymerizable compound containing the radical-polymerizable compound, further preferably to contain a radical-polymerizable compound containing 2 to 4 radical-polymerizable groups in one molecule, and a radical containing two radical-polymerizable groups in one molecule. It is particularly preferable to contain a polymerizable compound.
  • the radically polymerizable compound A includes an aromatic ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms) and an alicyclic ring (preferably 3 to 24 carbon atoms, 3 to 18 carbon atoms). It is more preferable to contain at least one of 3 to 6), and it is further preferable to contain an aromatic ring.
  • the aromatic ring is preferably a benzene ring.
  • the molecular weight of the radically polymerizable compound A is preferably 100 to 900.
  • Examples of the radically polymerizable group contained in the radically polymerizable compound A include an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
  • the radically polymerizable compound A is also preferably a compound represented by the following formula (I-1).
  • L 20 is a 1 + q2-valent linking group, for example, a 1 + q2-valent group having an alcan structure (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms), and a group having an alken structure. (Preferably 2 to 12 carbon atoms, more preferably 2 to 6), a group having an aryl structure (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms). ), A group having a heteroaryl structure (preferably 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and examples of the heteroatom include a nitrogen atom, a sulfur atom, and an oxygen atom.
  • a 1 + q2-valent group having an alcan structure preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms
  • a group having an alken structure Preferably 2 to 12 carbon atoms, more preferably 2 to
  • 6-membered ring, 7-membered ring is preferable), or a linking group containing a group combining these.
  • group in which two aryl groups are combined include a group having a structure such as biphenyl, diphenylalkane, biphenylene, and indene.
  • group having a heteroaryl structure and a group having an aryl structure include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
  • L 20 is preferably a linking group containing at least one selected from a group having an aryl structure and a group having a heteroaryl structure, and more preferably a linking group containing a group having an aryl structure.
  • R 21 and R 22 independently represent a hydrogen atom or a methyl group, respectively.
  • L 21 and L 22 each independently represent a single bond or the above-mentioned linking group L, and are preferably a single bond or an alkylene group.
  • L 20 and L 21 or L 22 may be bonded to each other with or without the linking group L to form a ring.
  • L 20 , L 21 and L 22 may have the above-mentioned substituent T.
  • a plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different from each other.
  • Q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 1.
  • Examples of the radically polymerizable compound A include the compounds described in paragraphs 0017 to 0024 and Examples of JP-A-2014-090133, the compounds described in paragraphs 0024-0086 of JP-A-2015-009171, and JP-A-2015-070145.
  • the compounds described in paragraphs 0023 to 0037 of the publication, and the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016/152597 can also be used.
  • the content of the radically polymerizable compound A in the liquid film forming composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. It is more preferable to have.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less.
  • the content of the radically polymerizable compound A in the solid content of the liquid film forming composition is preferably 50% by mass or more, more preferably 75% by mass or more, and more preferably 90% by mass or more. More preferred.
  • the upper limit may be 100% by mass.
  • the radically polymerizable compound A may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the solid content of the liquid film forming composition is substantially composed of only the radically polymerizable compound A.
  • the content of the radically polymerizable compound A in the solid content of the liquid film forming composition is 99.9% by mass. This means that the content is 99.99% by mass or more, more preferably 99.99% by mass or more, and further preferably composed of only the polymerizable compound A.
  • the liquid film forming composition preferably contains a solvent (hereinafter, may be referred to as "liquid film solvent").
  • solvent for the liquid film
  • the liquid film forming composition preferably contains 90% by mass or more of the liquid film solvent, more preferably 99% by mass or more, and may contain 99.99% by mass or more.
  • the boiling point of the liquid film solvent is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and 130 ° C. or lower. Is even more preferable.
  • the lower limit is preferably 23 ° C, more preferably 60 ° C or higher.
  • the composition for forming a liquid film may contain a radical polymerization initiator.
  • the radical polymerization initiator include a thermal radical polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferable.
  • the photoradical polymerization initiator a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides.
  • the solid content of the liquid film forming composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and 2 to 5% by mass. Is more preferable.
  • the total amount thereof is preferably in the above range.
  • the liquid film forming composition may contain one or more of a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant and the like.
  • the method for synthesizing the silicone-containing acrylate resin contained in the precursor composition B-3 is as follows. Methyl silicone resin KR-500 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (110.8 parts), 2-hydroxyethyl acrylate (58.1 parts), p-toluenesulfonic acid monohydrate (0.034) After mixing the parts), the temperature was raised to 120 ° C., and the methanol produced by the condensation reaction was distilled off and stirred for 3 hours to react to obtain a silicone-containing acrylate resin. Further, the silicone-containing acrylate resins contained in the precursor compositions B-1, B-2 and B-4 can also be synthesized by the same method using the raw materials shown in the table.
  • the description in the column of "flow velocity (cm / h)" indicates the rate at which the precursor composition passes through the filter (filtration rate) in a state where the liquid flow is stable.
  • the speed at which the precursor composition passes through the filter is always lower than 0.9 cm / h (0.9 cm / h) in at least one of the filters.
  • the speed at which the precursor composition passed through the filter exceeded 0.9 cm / h for a total of 20 seconds, but continuously exceeded 10 seconds or more.
  • the description in the column of "pressure (MPa)" indicates the filtration pressure in the filtration step. Further, in all the examples, the maximum speed at which the precursor composition before filtration or the composition for forming an imprint pattern after filtration was provided was 0.2 cm / h or more.
  • the particle size is The number of foreign substances of 0.18 ⁇ m or more and less than 0.20 ⁇ m is shown. The same applies to other numerical ranges.
  • Particle increase (Number of particles after standing)-(Number of particles before standing)
  • the number of particles the number of particles having a particle diameter of 0.20 ⁇ m or more in 1 mL of the imprint pattern forming composition or the comparative composition was measured. The evaluation results are shown in the column of "Number of foreign substances after aging (pieces / mL)" in the table below.
  • Example or Comparative Example the imprint pattern forming composition or the comparative composition was ejected from the nozzle 20 times in a row using the inkjet printer DMP-2831, and the presence or absence of ejection failure due to clogging of the nozzle was confirmed. ..
  • the discharge failure means a phenomenon in which the composition discharge amount from the nozzle tip per unit time decreases when compared with the initial discharge.
  • the evaluation was made according to the following evaluation criteria, and the evaluation results are described in the column of "inkjet ejection failure" in the table. However, in the example described as "-" in the evaluation result column, the inkjet ejection defect was not evaluated.
  • a silicon wafer having a diameter of 300 mm was prepared, and particles having a diameter of 50 nm or more existing on the silicon wafer were detected by a defect detection device (SP-5 manufactured by KLA Tencor) on the wafer surface. This is the initial value of the number of defects.
  • the following composition for forming an adhesive layer C-1 was spin-coated on the silicon wafer and heated to 220 ° C. using a hot plate to form an adhesive layer on the silicon wafer.
  • the number of defects (the number of particles having a diameter of 50 nm or more existing on the silicon wafer) was measured by the same method. This is the measured value of the number of defects.
  • the difference between the initial value of the number of defects and the measured value of the number of defects was calculated.
  • the results obtained were evaluated based on the following criteria and the results are shown in the "Applying Defects" column in the table.
  • D The difference between the measured value of the number of defects and the initial value was 501 or more.
  • composition C-1 for Forming Adhesive Layer The components shown in the table below were mixed and filtered through a polytetrafluoroethylene filter having a pore size of 0.1 ⁇ m to obtain a composition for forming an adhesive layer.
  • the quartz mold As the quartz mold, a quartz mold having a line width of 20 nm and a depth of 55 nm with a line / space was used.
  • the composition for forming an adhesive layer C-1 was spin-coated on a silicon wafer and heated to 220 ° C. using a hot plate to form an adhesive layer on the silicon wafer.
  • a silicon wafer (silicon) on which the adhesion layer is formed is used as an inkjet device using an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix.
  • the composition for forming an imprint pattern was applied onto the substrate) by an inkjet method to form a pattern forming layer.
  • the composition for forming an imprint pattern is spin-coated on a silicon wafer (silicon substrate) on which the adhesion layer is formed. It was applied by the method to form a pattern forming layer having a thickness of 100 nm.
  • the quartz mold was brought into contact with the surface of the pattern forming layer on the side opposite to the silicon wafer, and the pattern forming layer was sandwiched between the quartz mold and the silicon wafer in the helium atmosphere. After exposure from the quartz mold side using a high-pressure mercury lamp under the condition of 100 mJ / cm 2 , the quartz mold was released to obtain a pattern on a silicon wafer.
  • the obtained pattern was observed with a scanning electron microscope, and the peeling of the pattern was evaluated according to the following evaluation criteria.
  • the evaluation results are described in the "Pattern formation" column of the table below.
  • D The region where the pattern was defective was less than 10% of the pattern forming area.
  • a predetermined pattern corresponding to the semiconductor circuit was formed on the silicon wafer by using the imprint pattern forming composition obtained by the method for producing the imprint pattern forming composition according to each embodiment. Then, using this pattern as an etching mask, silicon wafers were dry-etched, and semiconductor elements were manufactured using the silicon wafers. There was no problem in the performance of any of the semiconductor devices. Further, using the imprint pattern forming composition of Example 1, a semiconductor device was produced on a substrate having an SOC (spin-on carbon) layer by the same procedure as described above. There was no problem in the performance of this semiconductor device as well.
  • SOC spin-on carbon

Abstract

L'invention concerne un procédé de fabrication d'une composition de formation de motif d'impression, un procédé de fabrication d'un produit durci comprenant la composition de formation de motif d'impression, un procédé de fabrication d'un motif d'impression à l'aide de la composition de formation de motif d'impression, et un procédé de fabrication de dispositif comprenant le procédé de fabrication d'un motif d'impression. Les procédés comprennent une étape de filtration pour filtrer une composition de précurseur pour obtenir une composition de formation de motif d'impression. Dans l'étape de filtration, la vitesse à laquelle la composition de précurseur est passée à travers un filtre ne dépasse pas 0,9 cm par heure de façon continue pendant 10 secondes ou plus.
PCT/JP2021/032748 2020-09-09 2021-09-07 Procédé de fabrication de composition de formation de motif d'impression, procédé de fabrication de produit durci, procédé de fabrication de motif d'impression, et procédé de fabrication de dispositif WO2022054772A1 (fr)

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US18/179,820 US20230219280A1 (en) 2020-09-09 2023-03-07 Method for producing composition for forming imprint pattern, method for producing cured substance, imprint pattern producing method, and method for manufacturing device

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WO2023243484A1 (fr) * 2022-06-13 2023-12-21 キヤノン株式会社 Composition durcissable, procédé de formation de motif inversé, procédé de formation de film et procédé de production d'article
WO2024023743A1 (fr) 2022-07-28 2024-02-01 Resmed Sensor Technologies Limited Systèmes de détection d'une fuite dans un système de thérapie respiratoire

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WO2020175301A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Composition durcissable pour impression, kit, procédé de fabrication d'un motif, et procédé de fabrication d'élément à semi-conducteur

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WO2023243484A1 (fr) * 2022-06-13 2023-12-21 キヤノン株式会社 Composition durcissable, procédé de formation de motif inversé, procédé de formation de film et procédé de production d'article
WO2024023743A1 (fr) 2022-07-28 2024-02-01 Resmed Sensor Technologies Limited Systèmes de détection d'une fuite dans un système de thérapie respiratoire

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